Abstract

The continuing need for improved assessment of risk from heavy metal contamination of the environment has prompted scientific interest in quantifying and predicting metal solubility, ‘lability’ and bioavailability. This has led to the development of new techniques to fractionate and speciate trace metals in soils. The objectives of the current study were to increase understanding of the effects of (i) soil properties, (ii) contaminant source and (iii) contact time on metal lability and solubility in soils. Multi-stable isotope dilution (ID) methods were used to determine the lability (E-values) of Ni, Cu, Zn, Cd and Pb in soils, alongside more traditional approaches employed for metal fractionation including single and sequential extraction procedures. Most of the work was undertaken using (i) archived soils amended by metal salts (MA soils; n=23) and (ii) topsoils collected from Nottingham, Wolverhampton and London (Urban soils; n=100). The resulting data was used first to quantify the factors affecting trace metal lability in the MA soils using a logistic (S-shape) model which described metal E-value primarily as a function of soil pH with secondary influences from other soil properties. It was apparent that mineral oxides were important fixation phases for Ni, Zn and Cd while Pb was strongly affected by organic matter in soils. This model, parameterised on soils contaminated originally by metal nitrate solution, was then applied to the Urban soils to reveal the extent to which contaminant source still controlled metal lability. A further investigation of the long-term effect of metal source on metal lability was pursued through a third dataset of rural roadside soils (n=42) which had received Pb mainly from petrol-derived and geogenic sources, defined by their isotopic signature. It was demonstrated that petrol-derived Pb remained more labile than Pb from the parent material, despite decades of contact, although both petrol-derived and geogenic Pb contributed to both the labile and non-labile fractions. In a fourth dataset, soils that had received Pb from sewage sludge amendment (n=16), the co-existence of high phosphate concentration from sewage sludge limited the magnitude and range of Pb lability, probably through formation of Pb-phosphate minerals. No consistent agreement was found between labile fraction of Pb and any single sequential extraction (SEP) fraction in all soils contaminated by Pb from multiple sources.

Both empirical equations (extended Freundlich) and mechanistic models (WHAM-VII) were used to predict metal solubility in the MA and Urban soils. The advantage of using E-values (ME) over metal extractable by dilute nitric acid (MExt) to represent the reactive metal fraction in predictions of solubility was very clear for WHAM-VII, but not for the ‘locally parameterised’ Freundlich model. This was almost certainly due to the strong links between pH and E-value becoming subsumed into the coefficient nominally describing the direct influence of pH on metal solubility in the extended Freundlich equation. However, overestimation of the solution concentration from WHAM-VII was observed for all five metals, and strongly correlated with soil pH. Fractionation information from WHAM suggested that the source of the model’s underestimation of metal binding most likely lay with errors in the description of metal binding by Fe and Mn oxides for Ni, Zn and Cd and humic acid (HA) for Cu. An additional factor is the absence of potential binding phases in the WHAM model, such as particulate CaCO3, and the greater diversity of active adsorbents in soils at high pH values.

WHAM is based on the assumption that all metal bound to HA is labile. However, in the current study, ‘non-labile’ Cu, Zn and Pb fractions were observed in suspensions of HA extracted from grassland and peat soils. These were quantified by measuring metal E-values and EDTA-extraction of HA-bound metal using size-exclusion chromatography (SEC) coupled to ICP-MS to separate free and HA-complexed metal forms. Evidence of time-dependent metal fixation by HA was found for all three metals during the course of a 40 and 160 day incubation study. The proportion of non-labile Cu held by HA could be 40-50%. The presence of a non-labile metal fraction held by HA may substantially invalidate the assumption of reversible equilibrium which is central to all current geochemical models of metal binding to humic substances.